为了提高CO2分离膜的性能,将多壁碳纳米管(MWCNTs)添加到天然橡胶(NR)中制备NR/MWCNTs混合基质膜.考察了MWCNTs含量对混合基质膜机械性能的影响,研究了MWCNTs含量、进料气压力和热交联时间对NR/MWCNTs混合基质膜CO2分离性能的影响,研究了膜的耐老化性能,探讨了混合基质膜的CO2传递机制.结果表明:随着MWCNTs的增加,混合基质膜的CO2渗透系数逐渐增加,而CO2/N2选择性先增加后减少;当MWCNTs与NR的质量比为2.0％,混合基质膜的气体分离性能达到最优,其CO2渗透系数和CO2/N2选择性分别为138 Barrer和12.5.随着压力的增加,膜的CO2渗透系数和CO2/N2选择性逐渐增加.当热交联时间为24 h,在压力为2 bar下,MWCNTs与NR的质量比为2.0％的NR/MWCNTs混合基质膜的CO2渗透系数和CO2/N2选择性分别为95 Barrer和16.8;且热交联的膜比未交联的混合基质膜具有更优异的耐老化性能,这是因为MWCNTs与NR形成紧密的交联网状结构.

Polyaniline-decorated halloysite nanotubes (PANI-d-HNTs) having a multilayer hollow tubular structure were incorporated into sulfonated poly(ether ether ketone) (SPEEK) to prepare high-performance mixed matrix membranes (MMMs) for CO2/N-2 separation. Scanning electron microscopy images revealed that PANI-d-HNTs were tightly wrapped by SPEEK chains. The strong interfacial interaction between PANI-d-HNTs and SPEEK, as confirmed by attenuated total-reflectance Fourier-transform infrared spectroscopy and differential scanning calorimetry, led to excellent miscibility between the polymer and halloysite nanotubes, which in turn, resulted in improved mechanical properties for the MMMs. The highest CO2 permeability of 1260 Barrer and a CO2/N-2 selectivity of 87 were achieved for MMMs loaded with 0.9 wt% PANI-d-HNTs; these values exceeded the Robeson's upper bound proposed in 2008, and were also much higher than those of MMMs containing 0.9 wt% HNTs, for which, a CO2 permeability of 1093 Barrer and CO2/N-2 selectivity of 74 were observed. It is proposed that PANI-d-HNTs with a multilayer hollow tubular structure can be used as high-speed facilitated channels for CO2 transport, where densely arranged secondary amine groups readily reacted with CO2 to facilitate transport in the MMMs. Importantly, durability testing indicated that MMMs loaded with 0.9 wt% PANI-d-HNTs maintained outstanding CO2 permselectivity for over 120 h, suggesting the superior stability of the membranes under mixed gas feed conditions.

以PVA为基体,综述了聚乙烯醇气体分离膜经接枝和共混改性对二氧化碳气体分离性能的影响.PVA膜的改性能调整膜的结构和形态,能提高PVA分离膜的渗透性和选择性,使其朝着对气体分离有利的方向发展.最后,对改性的PVA膜在气体处理领域的工业应用前景进行了展望.

Lamellar PANI@CNTs-GO materials were prepared by intercalating polyaniline-coated carbon nanotubes (PANI@CNTs) in graphene oxide (GO) layers to regulate the interlayer spacing. Mixed matrix membranes (MMMs) with tuned structures were achieved by coating a mixed dispersion of PANI@CNTs-GO and polyvinylamine (PVAm) on an asymmetric polysulfone (PSf) membrane for enhancing its CO2 separation performance. The Fourier-transform infrared spectroscopy results showed that PANI was successfully coated on the surface of the CNTs. The X-ray diffraction results confirmed the intercalation of GO sheets with PANI@CNTs. PANI@CNTs-GO was uniformly dispersed in PVAm, as confirmed by scanning electron microscopy. The attenuated total reflectance Fourier transform infrared spectroscopy results revealed that strong interfacial interactions were present between PVAm and PANI@CNTs-GO. The MMM loaded with 1 wt% PANI@CNTs-GO showed the best CO2 separation performance with a CO2 permeance of 170 GPU and a CO2/N-2 selectivity of 122.4 at 1 bar under the pure gas condition. These values were much higher than those of the pristine PVAm membrane (CO2 permeance = 73 GPU and CO2/N-2 selectivity = 45.7). This enhanced separation performance can be mainly attributed to the effect of the facilitated transport carriers from amine groups in the interlayer spacing and the molecular sieving effect of the interlayer spacing. The MMMs exhibited excellent long-term stability even under the mixed-gas conditions for over 300 h with a CO2 permeance of 264 GPU and a CO2/N-2 selectivity of 149.8.

Mixed-matrix membranes (MMMs) for CO2/N-2 separation were prepared by incorporating nickel-substituted ZIF-8 (Zn/Ni-ZIF-8) into a polyether-block-amide (PEBA2533) polymer, in which the Zn and Ni ions in Zn/NiZIF-8 have different affinities for CO2 based on p-complexation; these MMMs exhibited exceptional molecular sieving properties compared to ZIF-8-PEBA MMMs. Scanning electron microscopy revealed that Zn/Ni-ZIF-8 nanoparticles were small and uniformly distributed within the PEBA, and attenuated total reflectance Fourier-transform infrared spectroscopy revealed good interfacial compatibility between the Zn/Ni-ZIF-8 and PEBA; consequently these MMMs exhibited excellent mechanical properties. The 10% Zn/Ni-ZIF-8-PEBA MMM showed a high CO2 permeability of 321 Barrer, and a CO2/N-2 selectivity of 42.8 at 2 bar; these values were much higher than those of the 10% ZIF-8-PEBA MMM (266 Barrer and 33.8, respectively). We assume that different metal-ion affinities towards CO2 resulted in the asymmetric adsorption/desorption behaviour of these MMMs, which led to a significantly higher permselectivity for the Zn/Ni-ZIF-8-PEBA MMM. The MMM loaded with 10% Zn/Ni-ZIF-8 exhibited long-term CO2-separation-performance stability under mixed-gas conditions, with a CO2 permeability of 282 Barrer and a CO2/N-2 selectivity of 42.7. Moreover, the permselectivity of the 10% Zn/Ni-ZIF-8-PEBA MMM under pure-gas condition surpassed Robeson's upper bound reported in 2008.

制备高性能的气体分离膜,是实现CO2高效回收的关键.为了提高CO2分离膜的性能,将中空管状结构的埃洛石纳米管(HNTs)添加到聚乙烯胺(PVAm)中配制涂膜液,并将PVAm-HNTs涂膜液涂覆到聚砜(PSf)超滤膜上制备PVAm-HNTs/PSf混合基质膜.其中PSf超滤膜作为支撑层,PVAm-HNTs致密涂层作为功能层,功能层结构与形态对CO2分离具有关键作用.采用XRD、SEM对HNTs的结构与形态进行表征,并借助FTIR和SEM对膜的形态与结构进行分析.在进料气为纯气条件下,系统地研究了HNTs添加量、进料压力、PVAm-HNTs涂层厚度对PVAm-HNTs/PSf膜的CO2分离性能影响,并考察了混合基质膜的CO2/N2混合气分离性能.结果显示:在水溶液中显示正电性的PVAm与负电性的HNTs具有较好的界面相容性.HNTs添加量为1％(质量)、PVAm-HNTs湿涂层厚度为50μm的混合基质膜,表现出最优的CO2分离性能.在进料气压力为0.1 MPa、测试温度为25℃、CO2/N2(15/85,体积比)混合气进料的条件下,膜的CO2渗透速率为178 GPU,CO2/N2选择性为83;该膜具有较好的稳定性,经过120 h运行后,渗透性和选择性仍能保持稳定.

[Objective] Natural rubber for hot air drying technology has low production efficiency,whereas the microwave brings about scorched rubber easily.Herein,the hot air and microwave coupled drying technology was adopted to product quality stable natural rubber in order to meet the industrialization requirements.[Method] The moisture content of raw natural rubber was reduced to 5.92 ％ using hot air drying firstly,and then the mass weight reached constant by utilizing microwave drying.The effects of the hot air and microwave coupled drying on raw rubber properties,molecular weight,mechanical properties and thenno-oxidative aging resistance of vulcanizates were investigated.[Result] The raw rubber properties changed a little,in which only volatile matter content and plastic initial value were reduced slightly.The mechanical properties and thermo-oxidative aging resistance of vulcanizates were reduced slightly with increasing microwave power.In comparison with air hot drying,the tensile strength and elongation at break were reduced from 18.87 MPa and 966 ％ to 17.4 MPa and 850％ after 900 W microwave heating,whereas their the change rate were reduced from-18.88 ％ and-41.75 ％ to-49.06 ％ and-80.37 ％,respectively.[Conclusion]These changes were attributed to natural rubber molecular chain rupture and protein decomposition.

Ion-surface imprinting technology has been widely used to remove heavy metal ions existed in waste water,due to its high selectivity to the target ions and good chemical stability. In this paper, electroactive surface-imprinted composite film was prepared successfully using Pb2+ as the template ion, polyaniline(PANI)as the polymer matrix and hydroxylated carbon nanotubes(MWCNTs-OH)as imprinting substrate, during which,Pb2+ ions were eluted by applying constant positive potential to form imprinted cavities. The structures of MWCNTs-OH and imprinted film were characterized by Fourier transform infrared(FTIR)and X-ray diffraction(XRD). The Pb2+ ion separation performance of the film was studied by electrochemical quartz crystal microbalance(EQCM)and atomic absorption spectrophotometer (AAS).The results showed that the maximum ion exchange capacity of composite film was 359mg/g and had excellent selectivity for Pb2+at the presence of other heavy metals ions(Cd2+,Zn2+,Co2+,Ni2+), with the separation factor of Pb2+/Zn2+ reached 418.74. Besides, the film exhibited outstanding cycle stability and rapid adsorption/desorption properties. In conclusion, this novel ion-surface imprinted composite film can be used for the efficient separation and recovery of Pb2+ in wastewater.

The high performance poly(ether-block-amide) (PEBA2533) membrane was prepared by dry phase inversion method, and then used for separation of vanillin from dilute aqueous solutions in the pervaporation-crystallization coupling (PVCC) system. The structural morphology of PEBA2533 membranes were characterized by SEM. The effects of feed concentration and operating temperature on the pervaporation performances of membrane were investigated. The results showed that the swelling degree of PEBA2533 membrane increased with the increase of concentration. This indicated that PEBA2533 could preferentially adsorb vanillin. With the increase of the feed concentration, the flux of vanillin increased while the separation factor decreased slightly. The vanillin permeation flux and separation factor both increased as the operating temperature increased. The equation of Arrhenius indicated that vanillin was more sensitive to temperature than water. When the temperature of first condenser was controlled at 2℃ in the PVCC system, the flux of crystal vanillin in the first condenser was 39.52 g·m-2·h-1 and the purity was more than 99%.

为了解决天然橡胶加工中存在的干燥时间长、能耗高、环境污染和设备占地较大等问题,设计了一种热空气-微波耦合天然橡胶干燥机,以实现两种干燥方式优势互补,提升天然橡胶加工干燥技术水平.以胶乳级颗粒胶为研究对象,采用该设备研究了微波干燥和热空气-微波耦合干燥特性,及耦合干燥动力学.研究发现:当天然橡胶初始含水率高时,采用微波干燥容易使橡胶受热不均匀,从而发生内部局部过热,使胶粒发粘变坏,影响天然橡胶的性能;而采用热空气-微波耦合干燥,橡胶的干燥时间由单独用热空气干燥的415.8 min降至耦合干燥的107 min,且干燥过程传热比较均匀,得到的橡胶品质较好.根据天然橡胶的水分变化规律,建立了天然橡胶热空气-微波干燥动力学模型,其动力学模型为:MR=(1-a) exp (-0.0485t0.685)+(1-b)exp(-4.76× 10-76t35.905).

The copolymer P(AM-DMC), one kind of cationic polyacrylamide, was synthesized by using acrylamide (AM) and methacryloxyethyltrimethyl ammonium chloride (DMC) as monomers with ultraviolet initiation. The copolymer was characterized by Fourier transform infrared spectroscopy. The composition of the copolymer was determined from the chlorine content by silver nitrate titration. The effects of monomer feed ratio and conversion on the composition of copolymer were discussed. Reactivity ratios were determined by the Fineman-Ross, Kelen-Tudos and Yezrielev-Brokhina-Roskin methods, indicating that their positive order calculation results were very different with those of reverse order, when the reactivity ratios were determined by Fineman-Ross. However, their positive order and reverse order calculation results were similar when the reactivity ratios were determined by the Kelen-Tudos and Yezrielev-Brokhina-Roskin methods. Therefore, the reactivity ratios were determined using the average results of the Kelen-Tudos and Yezrielev-Brokhina-Roskin methods. The reactivity ratios of AM and DMC were 2.3398 and 0.2285, respectively. This result showed that the copolymerization of AM and DMC was a non-ideal random copolymerization. Furthermore, the content of AM segments decreased with the increase of AM feed content, but the content of DMC segments increased. Moreover, the sequence length distribution was irregular and narrow, because AM was prone to homopolymerization.

To improve mechanical and magnetorheological properties of magnetorheological elastomers (MREs), a facile method was used to fabricate high-performance MREs which consisted of the core–shell complex microparticles with an organic-inorganic network structure dispersed in an ethylene propylene diene rubber. In this work, the proposed magnetic complex microparticles were in situ formed during MREs fabrication as a result of strong interaction between matrix and CIPs using carbon black as a connecting point. The morphology of both isotropic (i-MREs) and anisotropic MREs (a-MREs) was observed by scanning electron microscope (SEM). The effects of carbonyl iron particle (CIP) volume content on mechanical properties and hysteresis loss of MREs were investigated. The effects of CIP volume content on the shear storage modulus, MR effect and loss tangent were studied using a modified dynamic mechanical analyzer under applied magnetic field strengths. The results showed that the orientation effect became more pronounced with increasing CIPs in the a-MREs, whereas CIPs distributed uniformly in the i-MREs. The tensile strength, tear strength and elongation at break decreased with increasing CIP content up to 40 vol.%, while the hardness increased. It is worth noting that the tensile strength of i-MREs and a-MREs containing 40 vol.% CIPs still had high mechanical properties as a result of good compatibility between complex microparticles and rubber matrix. The MR performance of shear storage modulus and damping properties of MREs increased remarkably with CIP content due to strong dipole–dipole interaction of complex microparticles. Besides, the hysteresis loss increased with increasing CIP content as a result of magnetic field induced interfacial sliding between complex microparticles.

Sulfonated carbon nanotubes (sCNTs) were prepared by reacting concentrated sulfuric acid with carbon nanotubes (CNTs) on the defect sites. Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) were used to characterize the morphology and structure of sCNTs, respectively. Subsequently, polyaniline (PANI)/nickel hexacyanoferrate (NiHCF)/sCNT interconnected composite films were electrodeposited on the platinum electrode by the one-step co-polymerization using cyclic voltammetry in an aqueous dispersion containing sCNTs. The effect of concentration of NiSO4 and K3Fe(CN)6 in the prepared solution on the morphology and structure of PANI/NiHCF/sCNTs composite films was studied by scanning electron microscopy (SEM), FTIR spectroscopy, and X-ray diffraction (XRD), respectively. The effect of concentration of NiSO4 and K3Fe(CN)6 in the prepared solution on polymerization and electrochemical performance was investigated by cyclic voltammetry (CV), galvanostatic charge/discharge tests, and electrochemical impedance spectroscopy (EIS). One-step electrodeposition mechanism was discussed deeply. It was found that sulfonic acid groups had been attached to surface of CNTs, and sCNTs had higher dispersibility than CNTs in an aqueous dispersion. The morphology of PANI/NiHCF/sCNTs interconnected composite films was remarkably influenced by the concentration of NiSO4 and K3Fe(CN)6. The tubular packing structure appeared with the low concentration of NiSO4 and K3Fe(CN)6 in prepared solution, while the beautiful coral-like interconnected structure exhibited with 0.04 mol L−1 NiSO4 and 0.04 mol L−1 K3Fe(CN)6, which was mainly attributed to the π–π* electron stacking effect among sCNTs, NiHCF, and PANI. The specific capacitance and electroactivity of PANI/NiHCF/sCNTs composite films increased markedly with the increase of concentration of NiSO4 and K3Fe(CN)6 in prepared solution. The specific capacitance of PANI/NiHCF/sCNTs composite film was 430.77 F g−1 with 0.04 mol L−1 NiSO4 and 0.04 mol L−1 K3Fe(CN)6 due to self-doping effect of sCNT in composite films. The cycle stability of PANI/NiHCF/sCNTs composite films was enhanced with the increase of NiSO4 and K3Fe(CN)6 in prepared solution.

A suitable preparation and use in the wet pavement marking paint, belongs to the field of fine chemicals and transportation, which is characterized as a way for the construction of road marking paint in a wet road surface, the component parts of component A and group B prepared, using the two parts a and B at a mass ratio of 1: 1 ratio, sprayed onto the road surface by a crosslinking reaction curing film forming aspect wet pavement marking paint and the preparation method of marking products. Since the two-component coating system configured to, A component and modified epoxy to initiators, the active component B is an acrylic resin and a reducing agent. A, B two parts in the road construction is completed by curing the film forming chemical reaction, while introducing an epoxy resin coating systems and as a film forming acrylate resin composition, taking into account both the excellent properties, the present invention increases the hydrogenated bisphenol a UV-resistant properties of the epoxy resin, epoxy coating reduces yellowing disadvantages.

The aim of the study was to prepare a poly (acrylamide-co-acrylic acid) macromolecule slow-releasing fertilizer (PMSF) by electrochemistry method. The acrylamide, acrylic acid and Urea were polymerized and grafted on the Ti/PbO2 electrode by adding the cerium (Ce(IV)) as initiator. Then after drying and smashing, the PMSF was obtained. The PMSF was characterized by infrared spectroscopy (IR) and thermo gravimetric Analysis (TG). The influence on concentrations of Urea and KH2PO4 were discussed. The contents of nitrogen, phosphorus and potassium in the PMSF were determined by the spectrophotometer. By simulating the process of release, the release mechanism of PMSF was obtained. The results showed that a new macromolecule slow release fertilizer which contends nitrogen, phosphorus and potassium can be prepared by electrochemical method. Both the IR and TG proved the existing of Urea in PMSF. The form of phosphorus and potassium in the MSRF existed by ions. The best technological parameters of the process were obtained: ω(AM)=9%,ω(AA)=4.1%,ω(Ce(IV)=1%,I=0.05,ω(Urea)=7.2%, ω(KH2PO4)=5.4%. The total contents of the nitrogen, phosphorus and potassium in the PMSF can achieve a content of 58.5%. Among which,nitrogen 32.5%, phosphorus 13%, potassium 13%. The effective components can release 80% within 60 days.

Polyaspartic acid/polyacrylic acid interpenetrating networks absorbent polymer(IPNAP) was prepared using polyaspartic acid(PAsp) and acrylic acid(AAc) as raw materials,potassium peroxydisulfate as initiator,N,N′-methylenebisacrylamide as crosslinking agent by two step synthetic method.The IPNAP was characterized by FTIR.Effects of mass ratio of AAc to PAsp,initiator amount,crosslinking agent amount,and neutralization degree of AAc on absorbing property of IPNAP were studied.The results indicated that when the mass ratio of AAc to PAsp was 1.0∶1,the initiator amount was 0.50%,the crosslinking agent amount was 0.40%,the neutralization degree of AAc was 75%,the absorbing property of IPNAP was the best with the absorbing ratio of 826 g·g-1 and 120 g·g-1in distilled water and normal saline,respectively.

A series of emulsions were prepared at 73℃ by emulsion polymerization with versatic acid 10 esters(VeoVa10)and vinyl acetate(VAc),using ascorbic acid and hydrogen peroxide as initiator,mixture of sodium dodecyl sulfate(SDS)and nonylphenol polyoxyethylene(OP-10)or the ethoxylated alkyl alcohol ether disodium sulfosuccinate(DNS-330)as emulsifier,and PVA as protective colloid.The effects of anionic-nonionic emulsifier(DNS-330) on the emulsion stability,apparent viscosity,and particle size distribution was investigated.Meanwhile,the different effects of DNS-330 and traditional mixed emulsifier SDS/OP-10 on emulsion properties were compared.The results indicated that VeoVa10/VAc emulsion containing DNS-330(2.0wt% of total monomer)as emulsifier had narrow particle size distribution and low apparent viscosity.The Ca2+ ionic、mechanical and storage stability of the emulsion were improved.During the stabilization of the emulsion,because of the influence of double-stability group on DNS-330,the particle was stabilized by the non-ionic group with the steric stabilization mechanism and the outside of the particle was stabilized by the anionic group,which provided repulsive force to the latex particles between two similarly charged electric double layers.Moreover,the emulsion stability was improved greatly due to the synergetic effects caused by from the electrostatic and steric stabilization mechanisms.

Glass transition temperature of polymers is designed by using Fox equation,and poly(methyl methacrylate-butyl acrylate) is synthesized by emulsion polymerization.Technology conditions are obtained with an apparatus of laser particle size distribution.The glass transition temperatures(Tg) of polymers are measured by means of a differential scanning calorimeter(DSC).The experimental results indicate that there are some errors between the measured value and design value of Tg.Therefore,the Fox formula is improved through average method and least squares method,and theoretical design and experimental results meet well.The effects of the ratio of resin matrix to conductive materials on membrane stability are emphatically investigated.The results of experiments indicate that the performance of electrothermal membrane could be improved by adding appropriate conductive material,and the membrane stability is highly dependent on the ratio resin matrix to conductive material.Conductive net is studied by means of scanning electron microscopy.The results show that the PTC effect of amorphous acrylic polymer is significant,and the NTC effect of conductive filler is eliminated in the process temperature rise.

The stability of a electrothermal membrane, which was prepared from water-soluble conductive ink based on conductive carbon black (CB), poly(vinyl alcohol) (PVA) and poly(vinyl acetate) (PVAc), has been studied. The effects of the ratio of resin matrix to conductive materials on membrane stability were emphatically investigated. The results of experiments indicated that the performance of electrothermal membrane could be improved by adding appropriate conductive material, and the membrane stability is highly dependent on the ratio resin matrix to conductive material. Under the favorite experimental conditions the electrothermal membrane expresses good electroconduction and stable performance.